Starter feed stream acidification in DMC-catalyzed process

ABSTRACT

The process of the present invention provides for the manufacture of lower molecular weight DMC-catalyzed polyols than is possible using non-acidified continuous addition of starter (CAOS) feeds, by adding excess acid to a starter feed stream over that required for mere neutralization of the basicity of the starter. The benefits of the invention also extend to starters which do not contain basicity. Polyether polyols made by the inventive process may be used to produce improved polyurethane products such as coatings, adhesives, sealants, elastomers, foams and the like.

FIELD OF THE INVENTION

The present invention relates in general to catalysis, and morespecifically, to the acidification of starter feed stream(s) in acontinuous addition of starter (CAOS) polyether polyol productionprocess to improve double metal cyanide (“DMC”) catalyst activity.

BACKGROUND OF THE INVENTION

Base-catalyzed oxyalkylation has been used to prepare polyoxyalkylenepolyols for many years. In such a process, a suitably hydric lowmolecular weight starter molecule, such as propylene glycol orglycerine, is oxyalkylated with one or more alkylene oxides, such asethylene oxide or propylene oxide, to form a polyoxyalkylene polyetherpolyol product. Because it is possible to employ a low molecular weightstarter, the build ratio (polyol weight/starter weight) is relativelyhigh, and thus the process effectively utilizes reactor capacity.Strongly basic catalysts such as sodium hydroxide or potassium hydroxideare typically used in such oxyalkylations.

Thus, most of polyoxyalkylene polyols useful in synthesis ofpolyurethane polymers, as well as those suitable for other uses, containsubstantial amounts of oxypropylene moieties. As those skilled in theart are aware, during base-catalyzed oxypropylation, a competingrearrangement of propylene oxide to allyl alcohol generatesmonofunctional species which also become oxyalkylated, producing a widerange of polyoxyalkylene monols with molecular weights ranging from thatof allyl alcohol itself or its low molecular weight oxyalkylatedoligomers to polyether monols of very high molecular weight. In additionto broadening the molecular weight distribution of the product, thecontinuous generation of monols lowers the product functionality. Forexample, a polyoxypropylene diol or triol of 2,000 Da equivalent weightmay contain from 30 to 40 mole percent monol. The monol content lowersthe functionality of the polyoxypropylene diols produced from their“nominal” or “theoretical” functionality of 2.0 to “actual”functionalities in the range of 1.6 to 1.7. In the case of triols, thefunctionality may range from 2.2 to 2.4. As the oxypropylation proceedsfurther, the functionality continues to decrease, and the molecularweight growth rate slows. For these reasons, the upper practical limitfor base-catalyzed polyoxypropylene polyol equivalent weight is justabove 2,000 Da. Even at those modest equivalent weights, the productsare characterized by low actual functionality and broad molecular weightdistribution.

The monol content of polyoxyalkylene polyols is generally determined bymeasuring the unsaturation, for example by ASTM D-2849-69, “Testing ofUrethane Foam Polyol Raw Materials”, as each monol molecule containsallylic termination. Levels of unsaturation of about 0.060 meq/g to inexcess of 0.10 meq/g for based-catalyzed polyols such as those describedabove are generally obtained. Numerous attempts have been made to lowerunsaturation, and hence monol content, but few have been successful.

In the early 1960's, double metal cyanide (“DMC”) complexes, such as thenon-stoichiometric glyme complexes of zinc hexacyanocobaltate, werefound which were able to prepare polyoxypropylene polyols with low monolcontents, as reflected by unsaturation in the range of 0.018 to 0.020meq/g. This represented a considerable improvement over the monolcontent obtainable by base catalysis.

In the 1970's, General Tire & Rubber Company, in U.S. Pat. No.3,829,505, described the preparation of high molecular weight diols,triols etc., using double metal cyanide catalysts. However, the catalystactivity, coupled with catalyst cost and the difficulty of removingcatalyst residues from the polyol product, prevented commercializationof the products.

In the 1980's, interest in such catalysts resurfaced, and improvedcatalysts with higher activity coupled with improved methods of catalystremoval allowed commercialization for a short time. The polyols alsoexhibited somewhat lower monol content, as reflected by unsaturations inthe range of 0.015 to 0.018 meq/g. However, the economics of the processwere marginal, and in many cases, improvements expected in polymerproducts due to higher functionality and higher polyol molecular weightdid not materialize.

In the 1990's, DMC catalysts were developed with far greater activitythan was theretofore possible. Those catalysts, described for example inU.S. Pat. Nos. 5,470,813 and 5,482,908, allowed commercialization ofDMC-catalyzed polyether polyols by ARCO Chemical Company under theACCLAIM tradename. Unlike the low unsaturation (0.015-0.018 meq/g)polyols prepared by prior DMC catalysts, these ultra-low unsaturationpolyols often demonstrated dramatic improvements in polymer properties,although formulations were often different from the formulations usefulwith conventional polyols. These polyols typically have unsaturation inthe range of 0.002 to 0.008 meq/g.

As those skilled in the art appreciate, one drawback of DMC-catalyzedoxyalkylation is the difficulty of using low molecular weight startersin polyether synthesis. Polyoxyalkylation of low molecular weightstarters is generally sluggish, and often accompanied by catalystdeactivation. Thus, rather than employing low molecular weight startermolecules directly, oligomeric starters are prepared in a separateprocess by base-catalyzed oxypropylation of a low molecular weightstarter to equivalent weights in the range of 200 Da to 700 Da orhigher. Further oxyalkylation to the target molecular weight takes placein the presence of DMC catalysts. However, it is known to those skilledin the art that strong bases deactivate DMC catalysts. Thus, the basiccatalyst used in oligomeric starter preparation must be removed bymethods such as neutralization, adsorption, ion exchange, and the like.Several such methods require prolonged filtration of viscous polyol. Theadditional steps associated with catalyst removal from the oligomericstarter can add significant process time, and thus cost, to the overallprocess. Furthermore, the higher molecular weight of the starter lowersthe build ratio of the process significantly, thereby decreasing reactorutilization.

Another drawback associated with oxyalkylation with DMC catalysts isthat a very high molecular weight component is generally observed. Thebulk of DMC-catalyzed polyol product molecules are contained in arelatively narrow molecular weight band, and thus DMC-catalyzed polyolsexhibit very low polydispersities, generally 1.20 or less. However, ithas been determined that a very small fraction of molecules, i.e., lessthan 1,000 ppm, have molecular weights in excess of 100,000 Da. Thisvery small, but very high molecular weight, fraction is thought to beresponsible for some of the anomalous properties observed with ultra-lowunsaturation, high functionality polyols. These ultra high molecularweight molecules do not significantly alter the polydispersity, however,due to the extremely small amounts present.

U.S. Pat. Nos. 5,777,177 and 5,689,012, disclose that the high molecularweight “tail” in polyoxypropylene polyols may be minimized by continuousaddition of starter (“CAOS”) during oxyalkylation. In batch andsemi-batch processes, low molecular weight starter, e.g., propyleneglycol or dipropylene glycol, is added continuously as thepolyoxyalkylation proceeds rather than all being added at the onset. Thecontinued presence of low molecular weight species has been found tolower the amount of high molecular weight tail produced, while alsoincreasing the build ratio, because a large proportion of the finalpolyol product is derived from low molecular weight starter itself.Surprisingly, the polydispersity remains low, contrary to an expectedlarge broadening of molecular weight distribution. In the continuousaddition process, continuous addition of starter during continuousrather than batch production was found to also result in less lowmolecular weight tail, while allowing a build ratio which approachesthat formerly obtainable only by traditional semi-batch processingemploying base catalysis.

Unfortunately, when glycerine, a widely used trifunctional starter, isemployed in either the batch-type continuous addition of starterprocess, or the continuous-type continuous addition of starter process,the DMC catalyst gradually deactivates, and often a polyether of thedesired molecular weight cannot be obtained, or when obtained, productcharacteristics such as amount of high molecular weight tail,polydispersity, etc., are less than optimal. It appears that in the lowmolecular weight range of about 260 to 2500, where the ratio of glycerinto propylene oxide is higher than it is when making high molecularweight polyols, glycerin and other low molecular weight starters can actas inhibitors and stress the catalyst. Any other effects may be moreevident under these stressed conditions. Because glycerine is derivedfrom plant or animal matter by base-dependent processes, it contains oneor more basic contaminants which may cause a loss of DMC catalystactivity. McDaniel et al., recognize this and teach in U.S. Pat. No.6,077,978, the addition of very small amounts (i.e., up to about 100ppm) of acid to the glycerine initiator prior to its introduction intothe reactor as continuously added starter to neutralize the basiccontaminants. Synthetic glycerin may have trace residues of base fromthe manufacturing process. Methods said to be useful other than theaddition of acid, according to the '978 patent, include adsorption byacid adsorbents, and ion-exchange to either neutralize the impurities orto exchange them for acidic moieties. The addition of acid, however, isthe preferred method of McDaniel et al. for increasing the DMCcatalyst's ability to resist deactivation during CAOS feeds at highCAOS/oxide ratios. The '978 patent states at col. 6, lines 55-58, that,“ . . . less than 100 ppm acid based on total low molecular weightstarter need be added, preferably about 5 ppm to 50 ppm, and mostpreferably about 10 ppm to 30 ppm” should be used. McDaniel et al. failto provide any teaching or suggestion to add greater amounts of acidthan that needed to neutralize basic contaminants of the glycerine.

It would be desirable to be able to utilize low molecular weight startermolecules for low molecular weight polyol production using DMCcatalysis. It would further be desirable to prepare DMC-catalyzedpolyols with minimal high molecular weight tail components. It would befurther desirable to prepare polyoxyalkylation polyols in high buildratios. However, these objectives cannot be met if catalyst deactivationoccurs.

SUMMARY OF THE INVENTION

Accordingly, the present invention provides a process for themanufacture of lower molecular weight DMC-catalyzed polyols than washeretofore possible using non-acidified continuous addition of starter(CAOS) feeds. An excess of acid over that required for neutralization ofthe basicity of a low molecular weight starter is added to a CAOS feedstream. The inventive process may permit the use of less catalyst for agiven process than was heretofore required. The polyether polyolsprovided by the process of the present invention may allow for theproduction of improved polyurethane products, such as coatings,adhesives, elastomers, sealants, foams and the like.

These and other advantages and benefits of the present invention will beapparent from the Detailed Description of the Invention herein below.

DETAILED DESCRIPTION OF THE INVENTION

The present invention will now be described for purposes of illustrationand not limitation. Except in the operating examples, or where otherwiseindicated, all numbers expressing quantities, percentages, OH numbers,functionalities and so forth in the specification are to be understoodas being modified in all instances by the term “about.” Equivalentweights and molecular weights given herein in Daltons (Da) are numberaverage equivalent weights and number average molecular weightsrespectively, unless indicated otherwise.

The present invention adds an excess of acid to a continuous addition ofstarter (CAOS) feed stream over that required for neutralization of thebasicity of a low molecular weight starter. It had heretofore beenthought that the addition of excess acid would have, at best no effect,and at worst a negative effect, as experiments in which DMC catalyst isexposed to phosphoric acid in glycerine during storage showed a markeddecrease in catalyst activity over time. The inventive processunexpectedly allows manufacture of lower molecular weight DMC-catalyzedpolyols (250 Da to 2,500 Da) than is possible using non-acidified CAOSfeeds. The present invention may also permit the use of less catalystfor a given process than heretofore required. Glycerin and other lowmolecular weight starters can act as inhibitors and stress the catalyst.The acid addition has a positive effect allowing the reaction to proceedto completion. This positive effect is unexpectedly observed even withstarters having little or no basicity.

The present invention, therefore, provides a process for thepolyoxyalkylation of a low molecular weight starter involvingestablishing oxyalkylation conditions in an oxyalkylation reactor in thepresence of a double metal cyanide catalyst, continuously introducinginto the reactor at least one alkylene oxide and a low molecular weightstarter acidified with at least one of an inorganic protic mineral acidand an organic acid, wherein the acid is in an amount in excess of 100ppm, based on the weight of the low molecular weight starter andrecovering an oxyalkylated low molecular weight starter polyetherproduct. The process may be conducted as a semi-batch process or as acontinuous addition process. In either case, the low molecular weightstarter feed stream, is acidified over and above the level of basicimpurities found in the starter. The present invention is also directedto the polyol made by the inventive process and polyurethane productsincorporating those polyols.

As used herein, the term “continuous” means a mode of addition of arelevant reactant in such a manner so as to maintain an effectiveconcentration of the reactant substantially continuously. Continuousstarter addition, for example, may be truly continuous, or may be inrelatively closely spaced increments. It would not detract from thepresent process to incrementally add a reactant in such a manner thatthe added material's concentration decreases to essentially zero forsome time prior to the next incremental addition. However, it ispreferred that the amount of catalyst be maintained at substantially thesame level, although the concentration will change as the alkylene oxideand starter are charged to the reactor, during the course of thecontinuous reaction. Incremental addition of reactant which does notsubstantially affect the nature of the product is still “continuous” asthat term is used herein.

In the inventive process, polyoxyalkylene polyols are prepared by theoxyalkylation of a low molecular weight starter, in the presence of adouble metal cyanide complex catalyst. In conventional batch processesemploying DMC catalysts, the entire initiator (starter) is addedinitially to the reactor, DMC catalyst is added, and a small percentageof the alkylene oxide feed is added. A significant pressure dropindicates that the catalyst has been activated. Alternatively, apreactivated master batch of catalyst mixed with initiator may be used.The reactor temperature is maintained at between 70° C. and 150° C., andthe remainder of propylene oxide added at relatively low pressure, i.e.,less than 10 psig. In the conventional process, oligomeric startershaving an equivalent weight in the range of 200-700 Da or higher aregenerally used.

Using the conventional process, by way of example, the preparation of a3,000 Da molecular weight polyoxypropylated glycerine triol may beachieved through oxypropylation of a 1,500 Da molecular weightoligomeric oxypropylated glycerine starter until a molecular weight of3,000 Da is achieved. The build ratio is 3,000 Da/1,500 Da or 2.0. Thislow build ratio cannot efficiently take advantage of reactor capacity,as some 40 percent of the total reactor capacity is used for starteralone. In addition, the product will have a small, but significantamount of a very high molecular weight (>100,000 Da) fraction. This highmolecular weight fraction (“tail”) is believed to contribute to foamcollapse in some polyurethane systems.

In the typical continuous addition of starter (“CAOS”) process,polyoxyalkylation is accomplished by addition of a smaller amount ofoligomeric starter together with catalyst and initial alkylene oxide foractivation as in the conventional process. However, in the continuousaddition of starter process, low molecular weight starter is added inaddition to alkylene oxide, preferably as a mixed reactor feed stream.The amount may be 1.8 weight percent based on the weight of the combinedlow molecular weight starter/alkylene oxide stream, as a non-limitingexample. As a result of the use of lesser amounts of oligomeric starterand continuous introduction of low molecular weight “monomeric” starter,a glycerine polyol of 3,000 Da molecular weight may be prepared athigher build ratios, for example, a build ratio of 5. The processefficiency is increased by approximately 100 percent based on propyleneoxide usage. The product also exhibits less high molecular weight tail.

The typical CAOS process described above works well when making highmolecular weight polyols (e.g. greater than 2500 Da), however, whenmaking lower molecular weight polyols (in the range of 250 to 2500 Da),the catalyst often partially or fully deactivates, particularly whereglycerine a common trihydric starter is used in the CAOS process. Thisis shown by an increase in propylene oxide pressure in the reactor. Thereaction slows or substantially ceases, and the product may not reachthe desired molecular weight. Products are found to have broadpolydispersities and a relatively higher amount of high molecular weighttail.

It has now been surprisingly discovered that addition of an excessamount of acid, i.e., an amount greater than that needed to merelyneutralize the low molecular weight starter's basicity, to the starterprior to its introduction into the reactor as continuously added starterallows use of low molecular weight starter(s) to produce polyols of lowmolecular weight (250 Da to 2,500 Da) without catalyst deactivation,without increasing the amount of high molecular weight tail and withoutappreciably increasing polyol polydispersity.

Low molecular weight starters useful in the inventive process includethose having molecular weights below 400 Da, more preferably below 300Da, which contain basic, DMC catalyst-deactivating impurities.Non-limiting examples of such low molecular weight starter moleculesinclude glycerine, diglycerol, and polyglycerol, all of which aregenerally prepared through the use of strong bases. Glycerine isgenerally obtained by the hydrolysis, or “saponification” oftriglycerides, while diglycerol and polyglycerol may be obtained bybase-catalyzed condensation of glycerine. Further examples of suitablelow molecular weight starter molecules include various methylolatedphenols and similar products prepared by the base-catalyzed reaction offormaldehyde with urea, phenol, cresol, and the like. The beneficialeffects of the invention unexpectedly extend as well to startermolecules which do not contain basicity, e.g., ethylene glycol,propylene glycol, dipropylene glycol, trimethylolpropane,pentaerythritol, sorbitol, sucrose, and the like.

The low molecular weight starter may be mixed with other starters aswell, e.g., ethylene glycol, propylene glycol, dipropylene glycol,trimethylolpropane, pentaerythritol, sorbitol, sucrose, and the like, toproduce co-initiated polyether polyols. Reactions where another starteror a lower oligomer are added all at once to the reactor is not a“continuous addition of starter” process. However, it must be understoodthat a final portion of oxyalkylation may, if desired, be conductedwithout addition of low molecular weight starter. This “finishing” stepallows for reduction of moderate molecular weight oligomers by providingsufficient reaction time for the last added low molecular weight starterto be oxyalkylated to a high molecular weight, thus minimizingpolydispersity.

Although virtually any organic or inorganic acid may be used in theprocess of the present invention, useful acids include, but are notlimited to, the mineral acids and the organic carboxylic acids,phosphonic acids, sulfonic acids, and other acids. Phosphoric acid ispreferred as a mineral acid, whereas citric acid and 1,3,5-benzenetricarboxylic acids may be useful as organic acids. Acid derivativeswhich are reactive with bases, such as acid chlorides and acidanhydrides and the like, are also useful. Organic acids such asphosphonic acids, sulfonic acids, e.g., p-toluene-sulfonic acid, and thelike, may also be used. Examples of mineral acids which are suitableinclude hydrochloric acid, hydrobromic acid, and sulfuric acid, amongothers, while useful carboxylic acids or their acidifying derivativesinclude formic acid, oxalic acid, citric acid, acetic acid, maleic acid,maleic anhydride, succinic acid, succinic anhydride, adipic acid,adipoyl chloride, adipic anhydride, and the like. Inorganic acidprecursors such as thionyl chloride, phosphorous trichloride, carbonylchloride, sulfur trioxide, thionyl chloride phosphorus pentoxide,phosphorous oxytrichloride, and the like are considered as mineral acidsherein.

The amount of acid added in the inventive process is in excess of thatneeded for the mere neutralization of the glycerine, i.e., greater than100 ppm, more preferably the amount of acid ranges from greater than 100ppm to 2,000 ppm, and most preferably 200 ppm to 300 ppm. The acid maybe added in the process of the present invention in an amount rangingbetween any combination of the above-recited values, inclusive of therecited values.

In the continuous version of the CAOS process, the reaction may beinitiated by use of an oligomeric starter, but once begun iscontinuously initiated by further oligomeric starter, preferably byrecycle of an oligomer or polymer from a later stage of the reaction.Alkylene oxide together with starter or low molecular weightoxyalkylation product is added at various points along the reactor whichmay, for example, be a tubular reactor (“multi-point addition”). Acontinuous stirred tank reactor (CSTR) or a back-mixed reactor may alsobe used.

The alkylene oxides useful in the inventive process include, but are notlimited to, ethylene oxide, propylene oxide, oxetane, 1,2- and2,3-butylene oxide, isobutylene oxide, epichlorohydrin, cyclohexeneoxide, styrene oxide, and the higher alkylene oxides such as the C₅-C₃₀α-alkylene oxides. Propylene oxide alone or mixtures of propylene oxidewith ethylene oxide or another alkylene oxide are preferred. Otherpolymerizable monomers may be used as well, e.g., anhydrides and othermonomers as disclosed in U.S. Pat. Nos. 3,404,109, 3,538,043 and5,145,883, the contents of which are herein incorporated in theirentireties by reference thereto.

The process of the present invention may employ any double metal cyanide(DMC) catalyst. Double metal cyanide complex catalysts arenon-stoichiometric complexes of a low molecular weight organiccomplexing agent and optionally other complexing agents with a doublemetal cyanide salt, e.g. zinc hexacyanocobaltate. Suitable DMC catalystsare known to those skilled in the art. Exemplary DMC catalysts includethose suitable for preparation of low unsaturation polyoxyalkylenepolyether polyols, such as disclosed in U.S. Pat. Nos. 3,427,256;3,427,334; 3,427,335; 3,829,505; 4,472,560; 4,477,589; and 5,158,922,the contents of which are incorporated herein in their entireties byreference thereto. The DMC catalysts more preferred in the process ofthe present invention are those capable of preparing “ultra-low”unsaturation polyether polyols. Such catalysts are disclosed in U.S.Pat. Nos. 5,470,813 and 5,482,908, 5,545,601, 6,689,710 and U.S.Published Patent Application No. 2004-0044240-A1, the contents of whichare herein incorporated in their entireties by reference thereto.Particularly preferred in the inventive process are those zinchexacyanocobaltate catalysts prepared by the methods described in U.S.Pat. No. 5,482,908.

The DMC catalyst concentration is chosen so as to ensure good control ofthe polyoxyalkylation reaction under the given reaction conditions. Thecatalyst concentration is preferably in the range from 0.0005 wt. % to 1wt. %, more preferably in the range from 0.001 wt. % to 0.1 wt. %, mostpreferably in the range from 0.001 to 0.01 wt. %, based on the amount ofpolyether polyol to be produced. The DMC catalyst may be present in theprocess of the present invention in an amount ranging between anycombination of these values, inclusive of the recited values.

EXAMPLES

The present invention is further illustrated, but is not to be limited,by the following examples. Although the inventive process is describedbelow using glycerine as the starter, it is equally applicable to otherlow molecular weight starters which are synthesized, treated, or storedsuch that basic impurities which can cause DMC catalyst deactivation arepresent in the polyol, preferably starters having molecular weightsbelow 300 Da, more preferably below 200 Da. The present invention canalso be extended to those starters which do not contain basicimpurities.

Comparative and excess acidified oxypropylations employing continuousaddition of starter (CAOS) were performed in a 20 kg reactor. In eachcase, an amount of 700 Da molecular weight propoxylated glycerin startersufficient to provide a build ratio of 8 was introduced to the reactortogether with an amount of zinc hexacyanocobaltate complex DMC catalystsufficient to provide a final catalyst concentration of 30 ppm in thefinal product. Commercial glycerin and propylene glycol were utilized.

Following addition of oligomeric starter and catalyst, the reactor wasstripped with a nitrogen sparge at a pressure of 5 to 30 mm Hg for 30 to40 minutes and a reactor temperature of 130° C. Propylene oxide wasintroduced in an amount equivalent to 4 to 6 weight percent of thestarter charge and the reactor pressure monitored to ensure catalystactivation had occurred.

Pressure was allowed to drop below 500 torr prior to restarting thepropylene oxide feed. Following activation, propylene oxide in a “redhot” build ratio was added to the reactor. The “red hot” build ratio isdefined as the ratio of the amount of propylene oxide added plus theinitial starter weight to the initial starter weight.

The “red hot” build ratio is necessary to ensure the catalyst is fullyactivated before the glycerin or propylene glycol is introduced. Thefirst “red hot” build ratio refers to the build ratio when the propyleneglycol is started. The propylene glycol fed at a weight ratio of 2.3weight percent to the propylene oxide feed. The second “red hot buildratio refers to the start of the glycerin feed, at which point theglycerin was fed at a weight ratio of 17.1 percent to the propyleneoxide. The co-feed of glycerin, propylene glycol and propylene oxidecontinued until the reactor contents reached 60 percent of the finalbatch weight (a 40% non-CAOS cap for propylene glycol). At this point,the propylene glycol feed was stopped, but glycerin and propylene oxidefeeds continued. The co-feed of propylene glycol and propylene oxidecontinued until the reactor contents reached 90 percent of the finalbatch weight, at which point the glycerin feed was stopped (a 10%non-CAOS cap for glycerin). The propylene oxide feed was continued untilthe end of the batch. Reactor pressure was monitored throughout thebatch, and if the pressure exceeded 45 psia, the propylene oxide andCAOS feeds were cut off.

In Comparative Example C1, the glycerin was acidified with 60 ppm ofphosphoric acid. During this batch, the reactor pressure was 45 psiawhen the reactor contents reached 89 percent of the final batch weight,and the reactant feeds were shut down. Although 60 ppm of acid is morethan enough to neutralize the basic contaminants measured in theglycerin, the peak pressure during this batch was 43% higher than wasobserved during the batch in which the glycerin was acidified to 240 ppmphosphoric acid (Example 2). The batch of Example 2 completed normally,reaching a maximum pressure of 32 psia. The presence of a significantexcess of acid in Example 2 appears to have had a significant beneficialeffect on catalyst activity.

The results of these examples are summarized below in Table. I. TABLE IEx. C1 Ex. 2 Target molecular weight (Da) 700 700 Target OH# (mg KOH/g)238 238 Initial starter OH# (mg KOH/g) 238 238 Phosphoric acidconcentration in glycerin (ppm) 60 240 PG “red hot” build ratio 1.1 1.1Glycerin “red hot” build ratio 1.25 1.25 PG/Propylene oxide ratio duringCAOS feed 2.3 2.3 (%) Glycerin/Propylene oxide ratio during CAOS 17.117.1 feed (%) Final catalyst concentration in product (ppm) 30 30Reaction temperature (° C.) 130 130 Feed time (hours) 6 6 Overall buildratio 8 8 PG non-CAOS cap (%) 40 40 Glycerin non-CAOS cap (%) 10 10Maximum pressure during batch (psia) 46 32 (batch shut down)

The term “establishing oxyalkylation conditions” in an oxyalkylationreactor is believed to be self-explanatory. Such conditions areestablished when the reactor temperature, alkylene oxide pressure,catalyst level, degree of catalyst activation, presence ofoxyalkylatable compounds within the reactor, etc., are such that uponaddition of unreacted alkylene oxide to the reactor, oxyalkylation takesplace. As a non-limiting example, in the batch version of continuousaddition of starter, oxyalkylation conditions are initially establishedby following the procedures detailed in the preceding examples. By theterm “continuously introducing” with respect to addition of alkyleneoxide and glycerine starter is meant truly continuous, or an incrementaladdition which provides substantially the same results as continuousaddition of these components. By the term “oxyalkylated low molecularweight starter polyether” is meant a polyoxyalkylene polyether preparedby oxyalkylating the glycerine starter. The oxyalkylated glycerinestarter polyether will be a polyoxypropylated, glycerine-initiatedtriol. The terms “starter” and “initiator” as used herein are the sameunless otherwise indicated.

The polyether polyols produced by the process of the present inventionmay be reacted with one or more isocyanates to provide improvedpolyurethane products including, but not limited to, coatings,adhesives, sealants, elastomers, foams and the like.

The foregoing examples of the present invention are offered for thepurpose of illustration and not limitation. It will be apparent to thoseskilled in the art that the embodiments described herein may be modifiedor revised in various ways without departing from the spirit and scopeof the invention. The scope of the invention is to be measured by theappended claims.

1. A process for the polyoxyalkylation of a starter comprising:establishing oxyalkylation conditions in an oxyalkylation reactor in thepresence of a double metal cyanide (DMC) catalyst; continuouslyintroducing into the reactor at least one alkylene oxide and a starteracidified with at least one of an inorganic protic mineral acid and anorganic acid, wherein the acid comprises greater than about 100 ppm,based on the weight of the starter; and recovering an oxyalkylated lowmolecular weight starter polyether product.
 2. The process according toclaim 1, wherein the starter is chosen from glycerine, diglycerol andpolyglycerol.
 3. The process according to claim 1, wherein the starteris glycerine.
 4. The process according to claim 1, wherein the starteris chosen from ethylene glycol, propylene glycol, dipropylene glycol,trimethylol-propane, pentaerythritol, sorbitol and sucrose.
 5. Theprocess according to claim 1, wherein the acid is chosen from mineralacids, organic carboxylic acids, phosphonic acids, sulfonic acids andcombinations thereof.
 6. The process according to claim 1, wherein theacid is chosen from citric acid, 1,3,5-benzene tricarboxylic acids,phosphonic acids, p-toluenesulfonic acid, hydrochloric acid, hydrobromicacid, sulfuric acid, formic acid, oxalic acid, citric acid, acetic acid,maleic acid, maleic anhydride, succinic acid, succinic anhydride, adipicacid, adipoyl chloride, adipic anhydride, thionyl chloride, phosphoroustrichloride, carbonyl chloride, sulfur trioxide, thionyl chloridephosphorus pentoxide, phosphorous oxytrichloride and combinationsthereof.
 7. The process according to claim 1, wherein the acid isphosphoric acid.
 8. The process according to claim 1, wherein the acidcomprises greater than about 100 ppm to about 2,000 ppm, based on theweight of the starter.
 9. The process according to claim 1, wherein theacid comprises about 200 ppm to about 300 ppm, based on the weight ofthe starter.
 10. The process according to claim 1, wherein the reactoris a continuous reactor.
 11. The process according to claim 10, whereinthe continuous reactor comprises a tubular reactor.
 12. The processaccording to claim 10, wherein the step of continuously introducing theat least one alkylene oxide and the low molecular weight startercomprises multi-point addition.
 13. The process according to claim 10,wherein the continuous reactor comprises a back-mixed reactor.
 14. Theprocess according to claim 1, wherein the DMC catalyst is a zinchexacyanocobaltate.
 15. The process according to claim 1, wherein thealkylene oxide is chosen from ethylene oxide, propylene oxide, oxetane,1,2- and 2,3-butylene oxide, isobutylene oxide, epichlorohydrin,cyclohexene oxide, styrene oxide and C₅-C₃₀ α-alkylene oxides.
 16. Theprocess according to claim 1, wherein the alkylene oxide is propyleneoxide.
 17. The process according to claim 1, wherein the polyetherproduct has a molecular weight of about 260 Daltons (Da) to about 2,500Da.
 18. The process according to claim 1, wherein the process iscontinuous.
 19. The process according to claim 1, wherein the process issemibatch.
 20. A polyether polyol made by: establishing oxyalkylationconditions in an oxyalkylation reactor in the presence of a double metalcyanide catalyst; continuously introducing into the reactor at least onealkylene oxide and a low molecular weight starter acidified with atleast one of an inorganic protic mineral acid and an organic acid,wherein the acid comprises greater than about 100 ppm, based on theweight of the low molecular weight starter; and recovering anoxyalkylated low molecular weight starter polyether product.
 21. Thepolyether polyol according to claim 20, wherein the low molecular weightstarter is chosen from glycerine, diglycerol and polyglycerol.
 22. Thepolyether polyol according to claim 20, wherein the low molecular weightstarter is glycerine.
 23. The polyether polyol according to claim 20,wherein the starter is chosen from ethylene glycol, propylene glycol,dipropylene glycol, trimethylolpropane, pentaerythritol, sorbitol andsucrose.
 24. The polyether polyol according to claim 20, wherein theacid is chosen from mineral acids, organic carboxylic acids, phosphonicacids, sulfonic acids and combinations thereof.
 25. The polyether polyolaccording to claim 20, wherein the acid is chosen from citric acid,1,3,5-benzene tricarboxylic acids, phosphonic acids, p-toluenesulfonicacid, hydrochloric acid, hydrobromic acid, sulfuric acid, formic acid,oxalic acid, citric acid, acetic acid, maleic acid, maleic anhydride,succinic acid, succinic anhydride, adipic acid, adipoyl chloride, adipicanhydride, thionyl chloride, phosphorous trichloride, carbonyl chloride,sulfur trioxide, thionyl chloride phosphorus pentoxide, phosphorousoxytrichloride and combinations thereof.
 26. The polyether polyolaccording to claim 20, wherein the acid is phosphoric acid.
 27. Thepolyether polyol according to claim 20, wherein the acid comprisesgreater than about 100 ppm to about 2,000 ppm, based on the weight ofthe starter.
 28. The polyether polyol according to claim 20, wherein theacid comprises about 200 ppm to about 300 ppm, based on the weight ofthe starter.
 29. The polyether polyol according to claim 20, wherein thealkylene oxide is chosen from ethylene oxide, propylene oxide, oxetane,1,2- and 2,3-butylene oxide, isobutylene oxide, epichlorohydrin,cyclohexene oxide, styrene oxide and C₅-C₃₀ α-alkylene oxides.
 30. Thepolyether polyol according to claim 20, wherein the alkylene oxide ispropylene oxide.
 31. The polyether polyol according to claim 20, whereinthe DMC catalyst is a zinc hexacyanocobaltate.
 32. The polyether polyolaccording to claim 20, wherein the polyol has a molecular weight ofabout 260 Daltons (Da) to about 2,500 Da.
 33. In a process of producinga polyurethane by the reaction of at least one isocyanate and at leastone isocyanate reactive compound, the improvement comprising producingthe isocyanate reactive compound by establishing oxyalkylationconditions in an oxyalkylation reactor in the presence of a double metalcyanide (DMC) catalyst, continuously introducing into the reactor atleast one alkylene oxide and a low molecular weight starter acidifiedwith at least one of an inorganic protic mineral acid and an organicacid, wherein the acid comprises in excess of about 100 ppm, based onthe weight of the low molecular weight starter and recovering anoxyalkylated low molecular weight starter polyether product.
 34. In aprocess of producing one of a coating, adhesive, sealant, elastomer andfoam, the improvement comprising including the polyurethane according toclaim 33.